EP0704102A4 - Ensemble de faisceaux d'electrons pour le traitement de surface - Google Patents

Ensemble de faisceaux d'electrons pour le traitement de surface

Info

Publication number
EP0704102A4
EP0704102A4 EP94919218A EP94919218A EP0704102A4 EP 0704102 A4 EP0704102 A4 EP 0704102A4 EP 94919218 A EP94919218 A EP 94919218A EP 94919218 A EP94919218 A EP 94919218A EP 0704102 A4 EP0704102 A4 EP 0704102A4
Authority
EP
European Patent Office
Prior art keywords
electron beam
window
tube
electron
tubes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP94919218A
Other languages
German (de)
English (en)
Other versions
EP0704102B1 (fr
EP0704102A1 (fr
Inventor
George Wakalopulos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ushio Inc
Original Assignee
American International Technologies Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by American International Technologies Inc filed Critical American International Technologies Inc
Publication of EP0704102A1 publication Critical patent/EP0704102A1/fr
Publication of EP0704102A4 publication Critical patent/EP0704102A4/fr
Application granted granted Critical
Publication of EP0704102B1 publication Critical patent/EP0704102B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/30Electron-beam or ion-beam tubes for localised treatment of objects
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J5/00Details relating to vessels or to leading-in conductors common to two or more basic types of discharge tubes or lamps
    • H01J5/02Vessels; Containers; Shields associated therewith; Vacuum locks
    • H01J5/18Windows permeable to X-rays, gamma-rays, or particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/04After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J33/00Discharge tubes with provision for emergence of electrons or ions from the vessel; Lenard tubes
    • H01J33/02Details
    • H01J33/04Windows
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B29C2035/0877Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00Flat articles, e.g. films or sheets
    • B29L2007/008Wide strips, e.g. films, webs
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/34Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3462Cables
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/16Vessels
    • H01J2237/164Particle-permeable windows

Definitions

  • the invention relates to an arrangement of electron beam tubes having stripe-like beam patterns and, in particular, such an arrangement which forms a linear electron beam pattern for treatment of a surface.
  • electron beam tubes for treating and processing surfaces typically use 15 micron thick ti ⁇ tanium foil as the electron beam window. This requires a minimum operating voltage of 150 kilovolts in order to just penetrate the foil thickness. Typical voltages of at least 175 kilovolts are thus used to allow for the additional energy to process the substrate material.
  • An electron beam tube for surface treatment which avoids high voltages is a remote ion source type.
  • Such a tube generates a stripe-like electron beam which impinges on a surface in a stripe pattern.
  • the beam may be used for surface treatment of materials, such as cur ⁇ ing of adhesives, and radiation chemistry in general.
  • An example of this type of beam tube is found in U.S. Pat. No. 4,910,435 to G. Wakalopulos, assigned to the assignee of the present invention.
  • a long elec- tron beam source shown in Fig. 5 of the '435 patent, wherein a plurality of offset ion sources produce a plas ⁇ ma cloud at the center of a long chamber.
  • the long plas ⁇ ma cloud generates a long electron beam.
  • the present invention is concerned with this type of electron beam tube wherein a stripe-like beam is generated.
  • each beam tube generates a stripe-like electron beam which spans part of the width of material being treated at a relatively low beam voltage, i.e. as low as 15-30 kV.
  • the remainder of the width is treated with stripe-like beams from other tubes, the arrangement of tubes having beams spanning the entire width of material.
  • Thin tube windows being films or membranes strong enough to with ⁇ stand atmospheric pressure, allow lower power consumption and more efficient energy coupling.
  • a staggered array is used where tubes of constant diameter are stacked in offset geometries in order to attain wide beam spans as the substrate moves relative to the array.
  • a substrate may carry a substance to be cured, such as hot melt adhesive.
  • a present day problem with electron beam curing is the necessity of making the beam environment inert in order to eliminate oxygen inhibition of surface cure.
  • the beam tubes of the present invention can deliver suf ⁇ ficient energy for curing with low voltage electron beams delivered through thin window membranes. This reduces the requirement for inert environments and makes electron beam treatment through air much more cost competitive with ultraviolet light.
  • Preliminary tests indicate that polymerization, cross-linking, and scission differ in low voltage exposure to that of high voltage irradiation. Early tests show a favorable trend towards polymerization at lower electron energies produced by beam tubes of the present invention.
  • a tube to be used for the above purpose has a vacuum tube envelope with a base end through which elec- trodes are fed and a window end which is spaced opposite ⁇ ly from the base end.
  • a thin, electron beam permeable, carbide or nitride film, gas impermeable window is dis ⁇ posed in the window end.
  • the thin window is made using semiconductor thin film fabrication techniques.
  • a sili- con wafer is used as a substrate and a thin low pressure chemical vapor deposition (LPCVD) film or membrane of low-Z material, such as carbide or nitride or doped sili ⁇ con, is deposited on the substrate as a layer and then a small portion of the silicon wafer is etched away leaving the thin carbide or nitride layer supported by the sili ⁇ con wafer everywhere except where a window has been etched.
  • LPCVD thin low pressure chemical vapor deposition
  • a doped silicon membrane such as boron doped silicon could also be used. In this manner, the wafer -A -
  • the layer ad ⁇ heres to the silicon tenaciously so that a pressure dif ⁇ ference of at least an atmosphere between the inside and the outside of the tube may be withstood.
  • the wafer is trimmed so that only the window portion is used.
  • An extended filament disposed near the base of the tube provides a source of thermionic electrons.
  • An electron acceleration electrode in the form of a conduc ⁇ tive frame surrounding the window has a high positive voltage relative to a beam forming electrode which re ⁇ moves electrons from the vicinity of the filament and propels them toward the thin window after forming and shaping a beam which corresponds in dimensions to the window.
  • the beam forming electrode has a parabolic cy- lindrical shape, with the cylindrical axis parallel to the length of the extended filament. This electrode is negatively charged relative to the acceleration elec ⁇ trode, forcing electrons to form a cloud near the cylin ⁇ drical axis from where they are extracted by the acceler- ation electrode.
  • a plurality of similar tubes may be mounted with window ends of the tubes supported on a conductive plate in offset or staggered positions. Apertures in the plate correspond to windows of the tubes. The plate makes contact with a conductive rim of each window so that the plate can function as the beam acceleration electrode for each tube at a positive potential.
  • Elon ⁇ gate, stripe-like beams are aligned such that the totali ⁇ ty of beams from staggered tubes spans the width of mate- rial to be treated.
  • the tubes may be ar ⁇ ranged in the array so that the stripe-like beams form modular beam segments of any desired beam pattern. Such material to be treated is moved beneath the array of beams, either on a table or on rollers.
  • the stripe-like beams traverse an air atmosphere onto the surface of ma ⁇ terial to be treated.
  • the material is moved beneath the beams in a direction so that the beams are transverse to the direction of motion of the material.
  • the support plate for the tubes may accommodate a desired number of tubes so that a material of specified width may be treat ⁇ ed by the addition or removal of tubes from the support structure.
  • the beam tubes described herein are preferred for providing modular beam segments for a de ⁇ sired beam pattern, other types of tubes which generate stripe-like beam patterns and having thin, electron beam permeable, carbide or nitride film windows may be used, such as remote ion source tubes.
  • Fig. 1 is a cross-sectional view of a compact electron beam tube in accord with the present invention.
  • Fig. 2 is a cutaway orthogonal view of the electron beam tube of Fig. 1 taken along lines 2-2.
  • Fig. 3 is a top view of the electron beam tube of Fig. 1.
  • Figs. 4a and 4b are plan views of a method for making the thin windows for the electron beam tube of Fig. 1.
  • Fig. 5 is a perspective view of a tube array with multiple voltage leads mounted on a support plate in accord with the present invention.
  • Fig. 5a is a graph showing dose versus depth for a dual voltage tube array of the type shown in Fig. 5.
  • Figs. 6 and 7 are plan views of the tube arrays with movable material stages.
  • Fig. 8 is a plan view of a triangular array for treating linear material, such as cable or wire.
  • the electron beam tube 11 is shown having a vacuum tube envelope 13, which may be glass or ceramic, with a base end 15 and a window end 17, spaced apart and opposite from the base end.
  • a vacuum tube envelope 13 which may be glass or ceramic, with a base end 15 and a window end 17, spaced apart and opposite from the base end.
  • the entire tube is cylindrical, but the base end 15 has a larger circumference than the window end by approximately thirty percent.
  • the larger circumference of the base end accommodates tube pins 19.
  • a first pin 21 and a second hidden pin are connected to the tube en ⁇ velope by means of a metal-to-glass seal or feed-through carrying the electrodes 23, 25 into the center of the tube. These electrodes are supported from respective tube ends and provide mechanical support and electrical contact to a central extended filament 27.
  • This filament is a thermionic electron emitter operating at a relative- ly low voltage, such as 24 volts.
  • Tube pins 31, 33 provide mechanical support for an insulative sleeve 35 which provides support for an electron beam forming electrode 37.
  • a negative voltage relative to the filament of approximately minus 50-80 kV i s carried on a wire 39 running through the center of the tube to the electron beam forming electrode 37. Voltages as low as 15-30 kV may be used with very thin windows. The upper limit of desirable voltage is about 120 kV.
  • This beam forming electrode has the function of directing electrons from the extended filament 27 into an elongated central region of the electrode, by repulsion from the electrode walls.
  • the beam forming electrode is a para ⁇ bolic cylinder so that a long stripe-like electron beam, parallel to the filament, is formed.
  • the wire 39 is seen to be connected to a tube end 41 after exiting the tube envelope by means of a feed-through.
  • the tube envelope is maintained in a vacuum after being pumped down and sealed off by means of a glass seal 43.
  • the tube can be pumped down to a pressure of 10 Torr prior to sealing.
  • the tube may have an off-on control grid, not shown, for switching the beam off and on.
  • a thermionic filament tube has been shown, an indirectly heated cathode tube could also be used.
  • a tube window 51 Opposite the extended filament is a tube window 51, made of a thin low-Z layer which is electron beam permeable, but impermeable to gas.
  • win ⁇ dow 51 maintains a gas-tight seal, keeping the outside atmosphere from penetrating the interior of the tube.
  • the window is seated atop an opening 53 in the tube en ⁇ velope.
  • the window could be mounted from the inside of the tube envelope.
  • a rectangular conduc ⁇ tive frame is joined to the window allowing a positive voltage relative to the beam forming electrode to extract the electron beam from the tube. This voltage, which is ground potential, a high positive potential relative to the beam forming electrode, accelerates electrons from the beam forming electrode toward the window.
  • the conductive support frame connected to the periphery of the window carries ground voltage to bound ⁇ ary of window 51 providing an electric field through the window which attracts electrons from beam forming elec ⁇ trode 37.
  • Local ground potential is supplied by a mount- ing plate, discussed below, or from any convenient source.
  • the tube envelope 13 is glass or other dielec ⁇ tric, allowing penetration of the electric field from the boundary of window 51 into the vicinity of electrode 37.
  • the ground voltage is about 50,000 volts positive rela- tive to the beam forming electrode, thereby establishing an electric field between the interior of the beam form ⁇ ing electrode and the window. Since the window is elec ⁇ tron permeable, electrons from electrode 37 are projected through the window.
  • the conductive frame draws little current because substantially all electrons pass through the window.
  • the beam forming electrode 37 is seen to have a parabolic shape.
  • the parabola is elongated parallel to extended filament 27, so that the solid body of electrode 37 is a cylindri ⁇ cal parabola.
  • a pair of baffles 57 close a portion of the top of the electrode, but an elongated slit 59 ex ⁇ ists, allowing egress of a stripe-like beam which is ac- celerated toward the window 51.
  • the electron beam which is accelerated toward the window 51 is elongated in shape, parallel to extended filament 27.
  • the electrons, in a stripe pattern, are drawn to the high voltage coat ⁇ ing on the window and strike the window with sufficient energy to pass through the window, without attenuation.
  • the top face 52 of the tube is seen mounting window 51.
  • the window In one direction the window has an elongated dimension 61 while at right angles there is a narrower widthwise dimension 63.
  • the elongated dimension of the window is aligned with the corresponding dimension of the beam.
  • the window consists of a support portion 65 mounted atop an opening in the end of the tube, surrounded by a conductive frame 75.
  • the thin window 51 is in the central portion of the sup- port 65 and has dimensions of several millimeters wide by 1 to 8 inches in length. More practical lengths will be 1-3 inches, which is better suited for mass production.
  • the thickness of the thin window is in the range of 3 mi ⁇ crons to 7 microns.
  • Support 65 is made of silicon as described below. Metal and ceramic supports are also feasible.
  • a silicon wafer 71 has a very thin silicon or nitride coating applied by low pressure chemical vapor deposition. Fabrication of a thin film electron window is described in an article entitled "Electron Window Cathode Ray Tube Applications" by L. Hanlon et al. in J. Vacuum Science Technology Bulletin, 4(1) , Jan/Feb. 1986. In that article, coatings of sili- con carbide, boron nitride and boron carbide are de ⁇ scribed. However, the windows contemplated in the present invention are much smaller in the lengthwise di ⁇ rection than the CRT windows described in the article.
  • a conductive frame 75 seen in Fig. 3, which may be an aluminum plate to be used in mounting the tubes on a support plate so that a thin window faces in a desired direction.
  • Frame 75 is maintained at ground potential which is nominally zero volts. This is a relatively high voltage compared to the beam forming electrode 37 and so electrons are accelerated toward the window and projected through it.
  • Windows may also be made by doping a silicon wafer with a moderate amount of boron, then etching as above, leaving a boron doped silicon membrane, with a thickness less than 20 microns.
  • Fig. 4a shows the construction of the thin win ⁇ dow where a carbide or a nitride layer 73 is chemically vapor deposited on a silicon wafer 71 to a thickness of between 3 to 20 microns.
  • Windows of boron nitride, silicon carbide, silicon nitride, boron carbide, and bo ⁇ ron nitride hydride are preferred.
  • films may be made by evaporation, etch- ing and cathodic arc vapor deposition.
  • the silicon wafer 71 is etched with a groove 77. Through this groove, the electron beam passes and penetrates win ⁇ dow 73 in the zone immediately adjacent to groove 77.
  • Support 65 in Fig. 3 corresponds to a cut portion of waf- er 71 with dimensions corresponding to the outer dimen ⁇ sions of the window.
  • Other types of tubes such as re ⁇ mote ion source tubes, having similar windows, may be used.
  • a plurality of elec- tron beam tubes in rows 81-84 are shown mounted to a sup ⁇ port plate 91 in an array of 4 columns of 3 tubes per column. Neighboring columns are offset by one-half the distance between adjacent tubes in a column.
  • Support plate 91 is an insulative circuit board wherein each beam tube is electrically insulated from every other tube and is supported by the plate.
  • a conductive trace 85 extends to each frame surrounding the thin window of each tube. By means of this trace, ground potential 86 is applied to the vicinity of the thin window of each tube. As men ⁇ tioned above, the ground potential is a high voltage relative to the beam forming electrode of each tube.
  • a current monitor 87 such as an ammeter, measures the amount of current drawn from ground to the tube. By measuring current levels, one can test the operability of each tube in an array. If no current or a very low cur ⁇ rent is being drawn by a tube in comparison to other tubes, this is an indication that the tube is not func- tioning properly and the entire array should be shut down until the defective tube is replaced. A single defective tube will impair the beam pattern unless redundant tubes are provided in an array. For large arrays a redundant row and column could provide a substitute tube for a de- fective one, without shutting down the array.
  • An array of tubes may be divided into a plural ⁇ ity of sections.
  • Fig. 5 shows the array divided into a first section consisting of rows 81 and 82 and the second section consisting of rows 83 and 84.
  • the beam forming electrode of rows 81 and 82 has a first voltage applied through cable 88, say 30 kV.
  • the second section has a higher negative voltage, say 60 kV applied by cable 89. Cables 88 and 89 carry appropriate voltages for all tube pins, not only the high voltage electrodes.
  • the first high voltage, 30 kV being a lower voltage, will affect primarily the surface of the material being treated.
  • the second high voltage, 60 kV being a higher voltage, will also affect the surface, but with a greater amount of penetrating power, will also affect a greater depth of material.
  • a treatment gradient may be formed, with greater treat ⁇ ment being at the surface and lesser treatment below the surface. It is considered important to have the greatest amount of treatment at upper levels of the surface in applications such as curing of hot melt adhesives.
  • the beams are projected through apertures in the plate, corresponding in size to each window.
  • the beams are staggered so as to sweep a continuous track across the substrate as the substrate moves under the beam tubes.
  • the track is a continuous swathe which will sweep the substrate as the substrate moves relative to the tube array as illustrated in Figs. 6 and 7.
  • the plot shows the penetration of a low voltage beam, about 30 kV, in plot 80 and the penetration of a high voltage beam, about 60 kV, in plot 82.
  • the two plots are summed to compute to ⁇ tal dose in a material.
  • the low voltage beam has a sig- nificant contribution at near zero depth and a rapidly diminishing contribution at just a few microns below the surface.
  • the substrate 101 is mounted on a table 103 which may move by means of rollers 105 and 107 in the X and Y directions respectively.
  • the beam tubes may be seen to be mounted face down on support plate 109 which is electrically grounded in order that the thin windows at the window end of each tube are at a high positive potential relative to the beam forming elec- trode.
  • the substrate 101 may be seen to have beam expo ⁇ sure regions 113 and 115. These beam traces, if they were in a straight line, would span the width of sub ⁇ strate 101 in a single track.
  • the beam traces appear to be segmented stripes which are offset from each other by a distance equal to the lateral separation of the beam tubes.
  • the entirety of the sub ⁇ strate may be treated with an electron beam having the width of a track established by beam segments 113 and 115.
  • the treatment area is a swathe extending from one edge 117 of the substrate to the opposite end 119.
  • the width of the swathe is equal to the length of the track established by segments 113 and 115.
  • the entire length and width of the substrate 101 could be treated with an electron beam exposure.
  • a web 121 is shown passing beneath a plate 123 having a plurality of elec- tron beam tubes mounted thereon, similar to those shown on plate 109 in Fig. 6.
  • These electron beam tubes, simi ⁇ lar to the beam tubes of Fig. 1, generate offset linear beam segments, 125 and 127.
  • These beam segments resemble offset stripes which, if placed in a single line would be a track extending across the width of the web 121.
  • the beam segments or stripes if considered in a single track, would span the width of web 121 and allow the entire width of the web to be irradiated with an electron beam.
  • a triangular support plate 151 is shown to have sides 153, 154 and 155. These sides mount three electron beam tubes 152, 156 and 158. These tubes are the same type as described with reference to Fig.
  • the array of tubes emit stripe-like electron beams 163, 164 and 165 which circumscribe the circumfer ⁇ ence of a cable 170 having a generally circular circum ⁇ ference, which is the surface being treated.
  • the dashed lines in the drawing indicate an exaggerated beam diver ⁇ gence from the tubes which are spaced apart, in air, from the cable surface to be treated.
  • the beams are seen to form a triangle tangent with the surface of the cable. Other shapes which are extruded or linear in character may be similarly treated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Electron Sources, Ion Sources (AREA)
  • Welding Or Cutting Using Electron Beams (AREA)
  • Electron Beam Exposure (AREA)
  • ing And Chemical Polishing (AREA)
EP94919218A 1993-05-26 1994-05-23 Ensemble de faisceaux d'electrons pour le traitement de surface Expired - Lifetime EP0704102B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US68052 1993-05-26
US08/068,052 US5414267A (en) 1993-05-26 1993-05-26 Electron beam array for surface treatment
PCT/US1994/005819 WO1994028573A1 (fr) 1993-05-26 1994-05-23 Ensemble de faisceaux d'electrons pour le traitement de surface

Publications (3)

Publication Number Publication Date
EP0704102A1 EP0704102A1 (fr) 1996-04-03
EP0704102A4 true EP0704102A4 (fr) 1996-06-12
EP0704102B1 EP0704102B1 (fr) 1998-08-05

Family

ID=22080124

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94919218A Expired - Lifetime EP0704102B1 (fr) 1993-05-26 1994-05-23 Ensemble de faisceaux d'electrons pour le traitement de surface

Country Status (10)

Country Link
US (2) US5414267A (fr)
EP (1) EP0704102B1 (fr)
JP (1) JPH08510864A (fr)
KR (1) KR100269911B1 (fr)
AT (1) ATE169424T1 (fr)
CA (1) CA2163554C (fr)
DE (1) DE69412261T2 (fr)
DK (1) DK0704102T3 (fr)
TW (1) TW257892B (fr)
WO (1) WO1994028573A1 (fr)

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ATE169424T1 (de) 1998-08-15
KR100269911B1 (ko) 2000-10-16
CA2163554C (fr) 2003-08-19
TW257892B (fr) 1995-09-21
USRE35203E (en) 1996-04-09
EP0704102B1 (fr) 1998-08-05
KR960702672A (ko) 1996-04-27
DK0704102T3 (da) 1999-05-03
WO1994028573A1 (fr) 1994-12-08
JPH08510864A (ja) 1996-11-12
CA2163554A1 (fr) 1994-12-08
EP0704102A1 (fr) 1996-04-03
DE69412261T2 (de) 1999-04-01
DE69412261D1 (de) 1998-09-10
US5414267A (en) 1995-05-09

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